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Description

RELATED APPLICATIONS

This application claims priority to German application No. 161 ! "1#.6$ %le& '(l.1)$ #**1.

+AC,GRO-ND O T/E IN0ENTION

1. iel& o the In2ention

The in2ention relates to a 3(4 salt composition or 3(4 5aths hich is accessi5leor partic(larly simple re7eneration an& &e erri8in7.

#. Description o the Relate& Art

To achie2e a hi7h9:(ality 8inc coatin7$ the or;pieces hich are to 5e 7al2ani8e&pass thro(7h a n(m5er o process steps prior to the hot9&ip 7al2ani8ation. A tera &e7reasin7 sta7e to remo2e or7anic contaminants an& a s(5se:(ent pic;lin7sta7e or the aci&ic remo2al o o4i&ic contaminants$ the or;pieces$ a terrinsin7$ pass thro(7h a pretreatment sta7e in a 3(4 5ath hich contains the3(4in7 a7ent sol(tion. The p(rpose o this 5ath is to protect the or;pieces romcorrosion on their ay to the 8inc 5ath an& &(rin7 &ryin7.

l(4in7 a7ent sol(tions are a:(eo(s salt sol(tions ith a salt content o ** to or e4ample ,Cl$ NaCl$ ?7Cl #$ CaCl #@. In thecase o lo 9 (me 3(4 salts$ in partic(lar salt mi4t(res$ hich$ ho e2er$ onacco(nt o the lo er pic;lin7 e ect are only sel&om employe&$ the ammoni(mchlori&e content is mostly replace& 5y ,Cl.

In the case o &ry 7al2ani8in7$ the 3(4 salt is applie& to the material to 5e7al2ani8e& 5y &ippin7 the or;piece into the 3(4in7 a7ent sol(tion. E2en &(rin7&ryin7 there is a certain pic;lin7 e ect on acco(nt o the ormation ohy&ro4o8inc aci&s. On &ippin7 into the 8inc pot$ the &rie&9on 3(4 salt is melte&.or the acti2ity o 3(4 salts$ it is important or their meltin7 point to 5e ell5elo the temperat(re o the 8inc 5ath >appro4imately !

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metho&s o the prior art are 7enerally 5ase& on (sin7 a m(ltista7e process inhich$ %rst o all$ the p/ is set to 5et een .< an& !$ an& then the &i2alent ironhich is present in the 3(4 5ath is precipitate& as iron>III@ hy&ro4i&e thro(7h thea&&ition o hy&ro7en pero4i&e $ an& is then separate& rom the 3(4in7 a7entsol(tion 5y %ltration in an operation hich is comple4 an& len7thy$ on acco(nt o

the strea;y consistency o these iron hy&ro4i&e 3ocs. Only some o the 3(4in7a7ent sol(tion can 5e re(se& in this metho&. A 2ariant on this metho&$ in hichin each case only some o the 3(4in7 a7ent sol(tion is treate& in a separateinstallation$ is &escri5e& in DE #* # II@ to iron>III@. This iron is 5on&e&in an ion e4chan7er$ pre era5ly (sin7 hy&rochloric aci&$ an& is ret(rne& to thepic;lin7 tan; a ter it has 5een separate& o(t as iron9la&en re9e4traction aci&. The3(4in7 a7ent sol(tion rom hich iron has 5een remo2e& is e& 5ac; to the 3(45ath a ter this metho& has 5een carrie& o(t. This metho& has the &ra 5ac; o5ein7 comple4 an& e4pensi2e an& not ens(rin7 that carrie&9o2er or7aniccontaminants are eliminate&.

A metho& hich allo s the acti2e materials containe& in the ol& 3(4es to 5ealmost completely reco2ere& an& the orei7n s(5stances$ in partic(lar iron an&or7anic contaminants$ to 5e :(antitati2ely separate& o(t$ has 5een propose& inthe prior art. Fith this metho&$ the principle o circ(lation thro(7h e4ternaltreatment is (se& to o5tain$ rom the ol& 3(4es$ a 3(4in7 a7ent sol(tion hich isas 7oo& as ne an& is re(se& in the 7al2ani8ation plants. Or7anic contaminantsare &estroye& or are concentrate& in a precipitation sl(rry$ the :(antitati2ele2els an& ha8ar&o(s potential o hich are consi&era5ly lo er than ith othermetho&s hich are ;no n rom the prior art. /o e2er$ or process en7ineerin7reasons this metho& can only 5e (se& to process ol& 3(4 sol(tions ith ironcontents o (p to #* 7=l$ hich re:(ires the 3(4 5ath to 5e chan7e& more

re:(ently$ hich is more than compensate& or 5y the economic an& ecolo7icala&2anta7es o complete recyclin7 o the 3(4 salt$ the lo poll(tant content othe aste sl(&7e an& the consi&era5ly impro2e& :(ality o 7al2ani8ation. In themetho&$ %rst o all hy&ro7en pero4i&e an& ammonia are a&&e& to the ol& 3(4 ina n(m5er o metho& steps$ in or&er to precipitate iron$ an& then the or7anicimp(rities are 5ro;en &o n 5y the a&&ition o potassi(m perman7anate. A terthe iron hy&ro4i&e sl(&7e has 5een %ltere& o(t$ man7anese>II@ hich is incl(&e&is o4i&i8e& to man7anese &io4i&e (sin7 hy&ro7en pero4i&e an& is separate& o(t5y %ltration$ ith the res(lt that$ (ltimately$ a 3(4in7 a7ent sol(tion hich is as7oo& as ne is o5taine&.

/o e2er$ this metho& o the prior art li;e ise in2ol2es a n(m5er o sta7es an& inpartic(lar is reliant on the ol& 3(4es 5ein7 reprocesse& centrally$ entailin7 hi7htransport costs$ an& ha2in7 to 5e ret(rne& to the 7al2ani8ation plants in li:(i&

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orm.

O+'ECTS O T/E IN0ENTION

There ore$ in 2ie o the increasin7 oc(s on 7al2ani8ation plants ith re7ar& to

en2ironmental protection an& the e orts ma&e 5y the 7al2ani8in7 operators tocarry o(t the recyclin7 o the 3(4in7 a7ent sol(tion (n&er their o n a(spices$ ano5Ject o the present in2ention is to pro2i&e a 3(4 salt composition hich allo ssimple recyclin7 o the 3(4in7 a7ent sol(tion in one step an& is not reliant one4ternal$ central recyclin7 installations. As a res(lt$ the 3(4 can 5e (se& e2en inmar;ets hich are not accessi5le or con2entional recyclin7 metho&s$ orreasons o transport costs$ or e4ample o2erseas co(ntries.

S-??ARK O T/E IN0ENTION

Accor&in7 to the in2ention$ the a5o2e o5Jects are achie2e& 5y a &e erri8in7 3(4salt composition or 3(4 5aths$ containin7 8inc chlori&e an& al;ali metal chlori&e$

hich contains at least one or more al;ali8in7 constit(ents an& one or moreconstit(ents hich$ in a:(eo(s sol(tion$ o4i&i8e iron>II@ to iron>III@.

DETAILED DESCRIPTION O T/E IN0ENTION

The reprocessin7 in one step simpli%es the metho& hich is (s(ally pre erre& in7al2ani8ation plants$ namely o a&J(stin7 the p/ (sin7 ammonia ater an&o4i&i8in7 (sin7 hy&ro7en pero4i&e. At the same time$ the 3(4 salt (se& ;eepsthe chemical composition o the 3(4in7 a7ent sol(tion constant. It is alsopossi5le to &ispense ith the operation o settin7 the 8inc chlori&e ammoni(mchlori&e ratio 5y a&&in7 8inc chlori&e po &er a ter an operatin7 time o a eee;s. Three or;in7 steps are replace& 5y one step$ consi&era5ly simpli yin7operation.

To set the &esire& ratio o 8inc chlori&e to al;ali metal chlori&e$ in or&er to ens(rea e(tectic >lo 9meltin7@ 3(4 salt mi4t(re on the material 5ein7 7al2ani8e&$ apre erre& em5o&iment o the 3(4 salt composition accor&in7 to the in2entioncontains a5o(t 1* to a5o(t "* 5y ei7ht$ pre era5ly a5o(t #< to a5o(t )* 5yei7ht$ partic(larly pre era5ly a5o(t

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Al;ali metal perman7anate$ especially potassi(m perman7anate$ isa&2anta7eo(s as an o4i&i8in7 constit(ent$ since it can o4i&i8e 5oth iron an&or7anic contaminants$ an& man7anese>II@ hich orms can 5e remo2e& a7ain asman7anese &io4i&e (sin7 metho&s hich are ;no n per se$ 5(t it is also possi5leto (se metal pero4i&es an&=or metal chlorates$ s(ch as 8inc pero4i&e or 8inc

chlorate$ as o4i&i8in7 constit(ents. The :(antity o perman7anate incl(&e& i&eally res(lts rom the stoichiometric&eman& or o4i&ation o all the incl(&e& iron>II@ to orm iron>III@. Conse:(ently$ acontent o rom a5o(t *.1 to a5o(t 1< 5y ei7ht$ pre era5ly a5o(t *.< to a5o(t1* 5y ei7ht$ partic(larly pre era5ly a5o(t 1 to a5o(t < 5y ei7ht$ o al;alimetal perman7anate$ in this case in partic(lar potassi(m perman7anate$ 5ase&on the 3(4 salt in the 3(4 salt composition$ is hi7hly a&2anta7eo(s.

A (rther pre erre& em5o&iment o the present in2ention relates to a 3(4in7a7ent sol(tion hich is (se& to treat iron9containin7 metal s(r aces prior to the7al2ani8ation an& contains a 3(4 salt o the a5o2e composition. In partic(lar$ this

3(4in7 a7ent sol(tion is to ha2e a concentration o less than a5o(t !* 7=l$pre era5ly less than a5o(t * 7=l$ an& partic(larly pre era5ly less than a5o(t #II@ to iron>III@$ e4cee&s the optim(m ran7e i theiron>II@ content o the ol& 3(4 is o2er a5o(t < to a5o(t !* 7=l$ in hich casecoolers ha2e to 5e (se&. There ore$ the reprocessin7 is e4pe&iently carrie& o(t attemperat(res o less than a5o(t 6* to a5o(t )*B C.$ since a5o2e thistemperat(re pro5lems arise in 7al2ani8ation plants as a res(lt o the e2aporationo ater.

D(rin7 operation o the 3(4 5ath or treatment o iron9containin7 metal s(r acesprior to the 7al2ani8ation$ hich comprises treatment o 3(4 5aths >ol& 3(4es@hich contain iron as a res(lt o iron carry9o2er rom stan&ar& operation$accor&in7 to the in2ention the 8inc chlori&e=al;ali metal chlori&e ratio an& the p/or iron precipitation an& the o4i&ation o iron>II@ to orm iron>III@ are carrie& o(tin one step 5y contin(o(s or &iscontin(o(s a&&ition o a 3(4 salt composition as&escri5e&. This consi&era5ly simpli%es the metho& compare& to the metho&shich are &escri5e& in the prior art an& can also 5e carrie& o(t on a&ecentrali8e& 5asis in the 7al2ani8ation plants$ e2en 5y (ntraine& sta .

To operate the 3(4 5ath$ the 3(4 salt composition may 5e (se& in soli& orm orha2in7 5een &issol2e& in ater 5e ore 5ein7 a&&e&. An optim(m e ect isachie2e& i $ to operate the 3(4 5ath ith the a&&ition o the 3(4 salt$ the p/ othe 3(4 5ath is set in a ran7e rom a5o(t .* to a5o(t !.

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EMA?PLES

E4ample 1

A stan&ar& 3(4$ hich has 5een s( ciently triale& in practice$ has a 7oo&5( erin7 action an& ens(res a p/ o rom to ."$ as selecte&. This 3(4 has5ecome ell esta5lishe& an& has 7aine& i&esprea& acceptance in 7al2ani8ationplants.

/a2in7 consi&ere& all the possi5le chemical in3(ences an& ha2in7 per orme& aris; assessment$ the o4i&i8in7 a7ent selecte& accor&in7 to the in2ention aspotassi(m perman7anate$ hich as a&mi4e& ith the 3(4.

To &etermine the re:(ire& concentration o potassi(m perman7anate an&(ltimately the 3(4 concentration to 5e employe&$ stan&ar& 2al(es rom ana2era7e 7al2ani8ation plant ere employe&.

Stan&ar& 0al(es

l(4 5ath si8e #* m $ correspon&s to appro4imately #! t ann(al thro(7hp(t omaterial to 5e 7al2ani8e&$ appro4imately 1**** t 3(4 salt cons(mption$appro4imately 1.< ;7=t o material to 5e 7al2ani8e& 1< t o 3(4 per year$ ann(aliron carry9o2er (p to #* 7 o e=l$ i.e. amo(nt o iron to 5e o4i&i8e& !** ;7=yearcarry9o(t loss *.< m per ee;.

A mi4t(re containin7 # o potassi(m perman7anate as selecte& or lar7e9scale in&(strial (se.

The 3(4 salt ha& the ollo in7 composition > 5y ei7ht@

crystalline@

< o 8inc o4i&e soli&

!* o ammoni(m chlori&e

# o potassi(m perman7anate

As a res(lt$ the le2els o iron o2er the co(rse o a e months o operation ere

p(she& to ar& 8ero$ so that the man7anese co(l& then 5e remo2e& rom the 3(45ath 5y (sin7 an e4cess o potassi(m perman7anate.

E4ample #

In 8inc chlori&e mo&e$ a 5atch o

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This 3(4 5ath pro2e& to 5e i&eal or carryin7 o(t the tests$ since in partic(lar theratio o 8inc chlori&e to ammoni(m chlori&e &e2iate& consi&era5ly rom theoptim(m ratio.

+e ore the start o 3(4in7$ the p/ o the 3(4 5ath as set to .* (sin7 1* ml o

correspon&in7 to Al in Ta5le 1@$hich correspon&s to the ee;ly carry9o(t loss o *.< m rom a stan&ar& 5ath o #* m .

The #< ml hich ha& 5een remo2e& ere toppe& (p a7ain 5y #< ml o a 3(4in7a7ent sol(tion accor&in7 to the in2ention in accor&ance ith E4ample 1$ ith aconcentration o !** 7 o 3(4=l or !** ;7=m $ hich is a stan&ar& operatin7concentration in a 7al2ani8ation plant$ ollo e& 5y stirrin7 or appro4imately 1ho(r.

A ter a e secon&s$ an intensi2e 5ro n color as orme&$ an& 2ery rapi&&ecantin7 too; place a ter the stirrin7 operation ha& en&e&. The p/ rose rom.* to .".

A ter one &ay$ a specimen as remo2e& an& the re&(ction o iron an& thecomposition o the 3(4 components ere teste& >c . A# in Ta5le 1@. The specimeno the ol& 3(4 sol(tion as mi4e& ith a e &rops o /Cl$ an& the p/ asrestore& rom #." to .*$ in or&er to sim(late the carry9o2er o /Cl.

This proce&(re as carrie& o(t a total o o(r times$ in or&er to sim(late the o(r9ee;ly operation o a 5ath. A ter each cleanin7 r(n$ an analysis >correspon&in7to A# to A< in Ta5le 1@ as carrie& o(t$ in or&er to monitor the &e erri8in7.

S(mmary o the Res(lts

Each time 3(4 as a&&e&$ the p/ rose rom appro4imately .* to appro4imately.". This is an optim(m le2el or iron>III@ hy&ro4i&e precipitation.

The 8inc chlori&e=ammoni(m chlori&e composition has not chan7e& si7ni%cantly.

or samples A! an& A< rom Ta5le 1$ it is possi5le to reco7ni8e a sli7htimpro2ement in the 8inc chlori&e=ammoni(m chlori&e ratio.

The le2els o iron &roppe& rom #6.)< 7=l to #*.! 7=l. +ase& on the carry9o2er:(antity o iron to 5e remo2e& o !"* ;7 per ann(m$ 1#) ;7 o iron ha2e 5eenseparate& o(t each month. Ta;in7 acco(nt o reshly carrie& o2er iron$appro4imately # 7=l per month$ 7i2en consistent (se o the &e erri8in7 3(4 the5ath o(l& 5e ree o iron ithin < months. O2er this time$ the man7anesecontent o(l& rise to 1*** ppm.

At the latest at this time$ this content co(l& 5e eliminate& 5y ormin7 ?nO # ithree ,mnO !.

The iron9 ree an& man7anese9 ree 5ath can then 5e operate&$ or e4ample$ or ayear (sin7 con2entional 3(4 salt. The &e erri8in7 step can 5e res(me& once aniron content o pre era5ly #* 7=l is reache& a7ain.

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A proce&(re hich in2ol2es one month o &e erri8in7 ollo e& 5y t o months(sin7 a con2entional 3(4 salt is also concei2a5le. In this case$ the increase inman7anese is re&(ce& a7ain as a res(lt o the man7anese 5ein7 &ischar7e&.

The &isco2eries hich ha2e 5een ma&e lea2e ample room to meter the 3(4es

(se& in s(ch a manner that they are acc(rately matche& to the re:(irements oany partic(lar 7al2ani8ation plant.

TA+LE 1 ?eas(rement report or the 3(4 5ath analyses. A1 A# A A! A< QnCl # * * # # * # * 7=l N/ ! Cl 1*# 1*# 1* 1*< 1*) 7=l e #6.) #